Coated electrode and method of making a coated electrode

ABSTRACT

An electrode having a substrate with a first layer covering at least a portion of the substrate, and a second layer covering at least a portion of the first layer is disclosed. The first layer includes a porous layer consisting of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten. The second layer includes iridium.  
     In a method according to the present invention, a substrate is provided. A first layer is provided over at least a portion of the substrate, and a second layer is provided over at least a portion of the first layer. The first layer includes a layer consisting of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten. The second layer includes iridium.

CROSS CLAIM TO RELATED APPLICATION

[0001] Priority is hereby claimed to U.S. Provisional Patent Application No. 60/169,370 filed on Dec. 7, 1999, and is hereby incorporated by this reference.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates generally to coated electrodes and methods of making such electrodes.

SUMMARY OF THE INVENTION

[0004] The present invention includes an electrode having a substrate with a first layer covering at least a portion of the substrate, and a second layer covering at least a portion of the first layer. The first layer includes a porous layer consisting of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten. The second layer includes iridium.

[0005] In a method according to the present invention, a substrate is provided. A first layer is provided over at least a portion of the substrate, and a second layer is provided over at least a portion of the first layer. The first layer includes a porous layer consisting of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten. The second layer includes iridium.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] For a fuller understanding of the nature and objects of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings, in which:

[0007]FIG. 1 is a cross sectional side view of an electrode according to the present invention;

[0008]FIG. 2 illustrates a method according to the present invention;

[0009]FIG. 3 shows an electron photo micrograph of a first layer according to the present invention; and

[0010]FIG. 4 shows an electron photo micrograph of a second layer according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011]FIG. 1 shows an electrode 10 according to the present invention. The electrode 10 has a substrate 13 with a first end 16 and a second end 19. The substrate 13 may include platinum, iridium or both. For example, the substrate may be approximately 90% platinum and approximately 10% iridium. Other bio-compatible metals, such as titanium, may be suitable materials for the substrate.

[0012] The first end 16 has a first layer 22 and a second layer 25. The first layer 22 includes a porous layer of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten. The metals forming the carbides, nitrides and carbonitrides are all elements of the fourth through sixth sub-groups of the periodic system and thus include the transition metals. Carbides and nitrides of these transition metals include titanium carbide, titanium nitride, zirconium carbide and tantalum nitride. The first layer may further include other layers such as a layer of titanium. The first layer 22 may contact a portion of the substrate 13.

[0013] The second layer 25 covers at least a portion of the first layer 22, and the second layer 25 may contact the first layer 22. The second layer 25 may be an outer surface of the electrode 10. The second layer 25 includes iridium, iridium oxide, or both.

[0014] In use, the second end 19 of the electrode 10 receives electricity to be delivered to the first end 16. The second end 19 may be electrically connected via an electrical conductor 28 to an energy source 31, such as an electrical pulse generator of a cardiac pacemaker 32. When connected to a cardiac pacemaker 32, the first end 16 senses signals from the heart and delivers the signals to the second end 19 where the signals are transmitted to the cardiac pacemaker 32 via the electrical conductor 28.

[0015] The present invention includes a cardiac pacing lead assembly. Such an assembly has an electrode, like that described above, wherein the second layer 25 is electrically connected to excitable cardiac tissue 34. The present invention also includes a cardiac pacemaker 32 having a pacing lead assembly connected to an electrical pulse generator, like those described above.

[0016]FIG. 2 illustrates aspects of a method of making an electrode according to the present invention. In the method, a substrate, such as that described above, is provided 100. The substrate may be etched 103 to provide an etched substrate. Etching 103 the substrate may be performed in a sputter chamber by radio frequency (“RF”) sputter etching. In one embodiment of the present invention, RF sputter etching occurs in an argon rich atmosphere.

[0017] A first layer is provided 106 over at least a portion of the substrate. To provide at least part of the first layer, an RF bias may be applied to the substrate while DC sputtering with titanium in the sputter chamber.

[0018] As noted above, the first layer includes a porous layer consisting of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten. For example, to provide a titanium nitride layer, DC sputtering with titanium may be carried out in a nitrogen rich atmosphere. In an embodiment of such a method, DC sputtering with titanium in a nitrogen rich atmosphere occurs for a period of time while an RF bias is applied to the electrode, for example via the substrate, and then for a period of time while no RF bias is applied to the electrode. Other embodiments of the present invention do not apply an RF bias to the electrode while sputtering with titanium in a nitrogen rich atmosphere.

[0019] A second layer is provided 109 on at least a portion of the first layer to provide the electrode. The second layer includes iridium, iridium oxide, or both, and may be provided using the sputter chamber.

[0020] An example of a method according to the present invention, begins by providing a clean 90% platinum 10% iridium substrate. The substrate may be cleaned by sonicating the substrate with detergent, and rinsing the substrate with deionized water. To aid in drying and cleaning, the rinsed substrate may be sonicated with acetone, and rinsed with 2-propanol.

[0021] The cleaned substrate is then placed in a sputter chamber, such as model number 8667 manufactured by Materials Research Corporation located in Orangeburg, N.Y. that has been modified to provide reactive sputtering capabilities. The chamber is evacuated to less than 5 micro torr. The substrate is then RF sputter etched at 500 watts in an atmosphere of 7.0 mtorr of argon for 18 minutes. The etched substrate is then direct current (“DC”) sputtered with titanium for 2 minutes at 1 kW, with an RF bias applied to the substrate. Then nitrogen is introduced into the chamber at a combined pressure of 7.5 mtorr. After 18 minutes, the RF bias is removed, and the substrate continues to be sputtered with titanium for several hours at 1 kW. FIG. 3 shows a surface of a titanium-containing layer made according to the present invention.

[0022] The sputter chamber, with the titanium and titanium nitride coated substrate therein, is then evacuated to less than 5 micro torr. The titanium nitride coated substrate is sputtered with iridium for 30 minutes at 250 W RF. After performing this method, the iridium layer was found to be 0.27 microns thick. When exposed to air, at least some of the iridium may oxidize to form iridium oxide. FIG. 4 shows a surface of an iridium-containing layer made according to the present invention.

[0023] It is known that low values of polarization contribute to lower threshold voltages for the pacing function of a cardiac packing electrode and of a defibrillation electrode. Low values of polarization also contribute to increased sensitivity for the sensing function of such electrodes. Low polarization may also contribute to greater efficacy in stimulation of other types of muscle tissue and in the detection of other electrical activity in the body. It is known that titanium nitride can be reactively sputtered to yield a morphology suitable for a low polarization coating on an electrode. Titanium nitride is widely used for electrode coatings, but there are concerns regarding the long-term stability of titanium nitride.

[0024] It is also known that iridium (which probably oxidizes to iridium oxide in air and more so after pulsing) or iridium oxide can lower the polarization of an electrode, although generally not to as low a value as titanium nitride. Furthermore, iridium and iridium oxide coatings on electrodes have been shown to prevent the growth of fibrotic tissue around such electrodes. However, neither iridium nor iridium oxide has the very desirable morphology of titanium nitride.

[0025] The present invention combines a layer of material selected from the group of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten, such as titanium nitride, with a layer of iridium, iridium oxide or both. In doing so, the present invention achieves low polarization and prevents the growth of fibrotic tissue. Furthermore, the present invention promotes the long-term stability of the first layer by coating it with a second layer.

[0026] Although the present invention has been described with respect to one or more particular embodiments, it will be understood that other embodiments of the present invention may be made without departing from the spirit and scope of the present invention. Hence, the present invention is deemed limited only by the appended claims and the reasonable interpretation thereof. 

What is claimed is:
 1. An electrode comprising: a substrate having a first end and a second end; a first layer covering at least a portion of the first end, wherein the first layer includes a layer of a material selected from the group of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten; and a second layer covering at least a portion of the first layer, wherein the second layer includes iridium.
 2. The electrode of claim 1 , wherein the first layer is made at least in part from a porous material.
 3. The electrode of claim 1 , wherein the second layer includes iridium oxide.
 4. The electrode of claim 1 , wherein the second layer is an outer surface of the electrode.
 5. The electrode of claim 1 , further comprising an electrical conductor electrically connected to the second end of the electrode.
 6. The electrode of claim 1 , wherein the substrate includes platinum.
 7. The electrode of claim 1 , wherein the substrate includes iridium.
 8. The electrode of claim 1 , wherein the first layer contacts the substrate.
 9. The electrode of claim 1 , wherein the second layer contacts the first layer.
 10. A cardiac pacing lead assembly, comprising: an electrode having a substrate with a first end and a second end, and having a first layer covering at least a portion of the first end of the substrate, and having a second layer covering at least a portion of the first layer, wherein the first layer includes a layer of a material selected from the group of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten, and wherein the second layer includes iridium; and an electrical conductor electrically connected to the second end.
 11. The lead assembly of claim 10 , wherein the first layer is made at least in part from a porous material.
 12. The electrode of claim 10 , wherein the second layer includes iridium oxide.
 13. The lead assembly of claim 10 , wherein the second layer is an outer surface of the electrode.
 14. The lead assembly of claim 10 , further comprising an electrical conductor electrically connected to the second end of the electrode.
 15. The lead assembly of claim 10 , wherein the substrate includes platinum.
 16. The lead assembly of claim 10 , wherein the substrate includes iridium.
 17. The lead assembly of claim 10 , wherein the first layer contacts the substrate.
 18. The lead assembly of claim 10 , wherein the second layer contacts the first layer.
 19. A cardiac pacemaker, comprising: an electrical pulse generator; and an electrode electrically connected to the pulse generator, the electrode having a substrate with a first end and a second end, and having a first layer covering at least a portion of the first end, and having a second layer covering at least a portion of the first layer, wherein the first layer includes a layer of a material selected from the group of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten, and wherein the second layer includes iridium.
 20. The cardiac pacemaker of claim 19 , wherein the first layer is porous.
 21. The electrode of claim 19 , wherein the second layer includes iridium oxide.
 22. The cardiac pacemaker of claim 19 , wherein the second layer is an outer surface of the electrode.
 23. The cardiac pacemaker of claim 19 , further comprising an electrical conductor electrically connected to the second end of the electrode, and electrically connected to the pulse generator.
 24. The cardiac pacemaker of claim 19 , wherein the substrate includes platinum.
 25. The cardiac pacemaker of claim 19 , wherein the substrate includes iridium.
 26. The cardiac pacemaker of claim 19 , wherein the first layer contacts the substrate.
 27. The cardiac pacemaker of claim 19 , wherein the second layer contacts the first layer.
 28. A method of making an electrode, comprising; providing a substrate; providing a first layer over at least a portion of the substrate to provide a coated substrate, the first layer being comprised at least in part of a layer of a material selected from the group of a carbide, nitride or carbonitride of at least one of the metals titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten; and providing a second layer over at least a portion of the first layer to provide the electrode, the second layer having iridium.
 29. The method of claim 28 , further comprising etching the substrate.
 30. The method of claim 29 , wherein etching the substrate includes RF sputter etching the substrate.
 31. The method of claim 29 , wherein etching the substrate is performed in an argon rich atmosphere.
 32. The method of claim 28 , wherein providing the first layer includes DC sputtering with titanium.
 33. The method of claim 32 , wherein DC sputtering with titanium is performed in an argon rich atmosphere.
 34. The method of claim 32 , wherein an RF bias is applied to the substrate while DC sputtering with titanium occurs.
 35. The method of claim 28 , wherein providing the first layer includes providing a nitrogen rich atmosphere and DC sputtering in the nitrogen rich atmosphere with a material selected from the group of titanium, vanadium, zirconium, niobium, molybdenum, hafnium, tantalum or tungsten.
 36. The method of claim 35 , wherein DC sputtering in the nitrogen rich atmosphere occurs while an RF bias is applied to the substrate.
 37. The method of claim 35 , wherein DC sputtering in the nitrogen rich atmosphere occurs for a period of time while an RF bias is applied to the electrode, and then for a period of time while no RF bias is applied to the electrode.
 38. The method of claim 28 , wherein providing the second layer is performed using an RF sputter chamber.
 39. The method of claim 28 , wherein the first layer contacts the substrate.
 40. The method of claim 28 , wherein the second layer contacts the first layer. 